Method for producing 1,9-nonane diol

Abstract

The present invention provides a novel method for producing 1,9-nonane diol, with which 1,9-nonane diol can be efficiently produced with little environmental burden. This method for producing 1,9-nonane diol includes: (1) a step for blowing ozone gas into oleyl alcohol in such a way that ozone gas is blown until the ozone gas concentration at an outlet exceeds half the ozone gas concentration at an inlet, and the acid value of a treated product that has been treated with the ozone gas is 15 mg KOH / g or less; and (2) a step for hydrogenating, in the presence of a nickel catalyst, the treated product that has been treated with the ozone gas.

Description

Process for producing 1,9-nonanediol

[0001] The present invention relates to a process for producing 1,9-nonanediol.

[0002] 1,9-Nonanediol is used as a raw material for polyesters, polyurethanes, and acrylic resins, and has properties that enable the production of resins with excellent hydrolysis resistance, flexibility, ductility, and low-temperature characteristics (see, for example, Patent Documents 1, 2, etc.). Conventionally, as a method for producing 1,9-nonanediol, a method of producing 2,7-octadien-1-ol using butadiene and water as raw materials and then producing it by a hydroformylation reaction with carbon monoxide and hydrogen is known (see, for example, Patent Documents 3 to 7). In addition, the conventional method for producing 1,9-nonanediol uses petrochemical raw materials and is not preferable from the perspective of global warming.

[0003] As a method for producing 1,9-nonanediol utilizing biomass raw materials, for example, a method has been reported in which oleic acid is oxidatively decomposed to produce azelaic acid, followed by reagent reduction using LiAlH ４ However, a large amount of reaction solvent (THF) and hydrochloric acid are used, resulting in a large environmental burden and being unsuitable for industrialization (see, for example, Non-Patent Document 1).

[0004] Japanese Patent Application Laid-Open No. 62-054717 Japanese Patent Application Laid-Open No. 8-239572 Japanese Patent Publication No. 63-10931 Japanese Patent Application Laid-Open No. 57-197238 Japanese Patent Application Laid-Open No. 58-140030 Japanese Patent Application Laid-Open No. 2-243639 Japanese Patent Application Laid-Open No. 03-287554

[0005] Biomacromolecules 2010, 11, 911-918

[0006] In view of the above situation, an object of the present invention is to provide a novel process for producing 1,9-nonanediol that can be produced with low environmental burden and high efficiency.

[0007] As a result of diligent research, the inventors discovered that by treating oleyl alcohol with ozone gas under predetermined conditions and then hydrogenating the resulting product using a predetermined catalyst, it is possible to produce 1,9-nonanediol efficiently with minimal environmental impact, thus completing the present invention. Furthermore, the novel method for producing 1,9-nonanediol discovered by the inventors is also applicable to biomass-derived raw materials.

[0008] The present invention is a method for producing 1,9-nonanediol, comprising: (1) a step of blowing ozone gas into oleyl alcohol, wherein the ozone gas is blown in until the ozone gas concentration at the outlet exceeds 1 / 2 of the ozone gas concentration at the inlet, and the acid value of the treated product treated with the ozone gas is 15 mg KOH / g or less (hereinafter sometimes abbreviated as "ozone gas blowing step"); and (2) a step of hydrogenating the treated product treated with the ozone gas in the presence of a nickel catalyst.

[0009] In the method for producing 1,9-nonanediol of the present invention, the nickel catalyst is preferably a Raney nickel catalyst and / or a supported nickel catalyst. Furthermore, the reaction temperature in step (2) hydrogenation is preferably 50 to 100°C. Furthermore, in the method for producing 1,9-nonanediol of the present invention, the temperature of the oleyl alcohol in step (1) blowing in ozone gas is preferably 40°C or lower. Furthermore, a solvent can be used in step (1) blowing in ozone gas and / or step (2) hydrogenation. Furthermore, the solvent is preferably an alcohol. Furthermore, in the method for producing 1,9-nonanediol of the present invention, it is preferable to carry out step (2) hydrogenation under hydrogen pressure conditions of 0.6 MPa or higher. Furthermore, it is preferable to carry out step (1) blowing in ozone gas and step (2) hydrogenation in the same reactor. Furthermore, it is preferable to carry out step (1) blowing in ozone gas and step (2) hydrogenation continuously in the same reactor. Furthermore, in the method for producing 1,9-nonanediol according to the present invention, it is preferable to subject the crude reaction product containing 1,9-nonanediol obtained in step (2) hydrogenation to distillation. Furthermore, it is preferable that the oleyl alcohol is biomass-derived oleyl alcohol.

[0010] This invention provides a novel method for producing 1,9-nonanediol efficiently with minimal environmental impact, and is also applicable to biomass-derived raw materials.

[0011] The present invention is a method for producing 1,9-nonanediol, comprising: (1) a step of blowing ozone gas into oleyl alcohol, wherein the ozone gas is blown in until the ozone gas concentration at the outlet exceeds 1 / 2 of the ozone gas concentration at the inlet, and the acid value of the treated product treated with the ozone gas is 15 mg KOH / g or less; and (2) a step of hydrogenating the treated product treated with the ozone gas in the presence of a nickel catalyst.

[0012] <(1) Step of blowing in ozone gas> This step involves blowing ozone gas into oleyl alcohol, in which the ozone gas is blown in until the ozone gas concentration at the outlet is more than half of the ozone gas concentration at the inlet, and the acid value of the treated material treated with the ozone gas is 15 mg KOH / g or less.

[0013] The oleyl alcohol mentioned above may be derived from petrochemicals, but it is preferable to use biomass-derived oleyl alcohol to reduce environmental impact.

[0014] The above biomass-derived oleyl alcohols include animal-derived oleyl alcohols and plant-derived oleyl alcohols, but plant-derived oleyl alcohols are preferred.

[0015] Examples of plant-derived oleyl alcohols include oleyl alcohol derived from safflower oil, sunflower oil, rapeseed oil, canola oil, olive oil, camellia oil, palm oil, and palm kernel oil. Among these, palm oil-derived oleyl alcohol and palm kernel oil-derived oleyl alcohol are preferred.

[0016] Generally available plant-derived oleyl alcohol is not 100% oleyl alcohol, but contains impurities such as cetyl alcohol and stearyl alcohol. The oleyl alcohol according to the present invention preferably has a purity of 80% or more oleyl alcohol, preferably 85% or more, and particularly preferably 90% or more.

[0017] In the above step (1) blowing in ozone gas, it is preferable that the ozone gas is blown into oleyl alcohol in a bubbling state.

[0018] In the above step (1) blowing in ozone gas, the temperature of the oleyl alcohol is preferably 40°C or lower. If the temperature exceeds 40°C, the acid value of the treated material treated with ozone gas will increase, which may adversely affect the nickel catalyst in the subsequent step (2) hydrogenation, or self-decomposition (abnormal heat generation) may occur during that step, making temperature control impossible. The above temperature is more preferably 20°C or lower.

[0019] The concentration of ozone gas to be blown in is not particularly limited, ranging from 10 to 250 g / m². ３ While it can be used within this range, low concentrations result in longer ozone gas injection times, and excessively high concentrations cause abnormal heat generation, making temperature control difficult. In other words, the preferred range for ozone gas concentration is 30 to 200 g / m³. ３ More preferably, 40 to 150 g / m² ３ That is the case.

[0020] The time for blowing in the ozone gas is not particularly limited, but it is usually preferable to do so for 2 to 8 hours.

[0021] The amount of ozone gas to be injected can be determined by measuring the ozone concentration at the injection port and the ozone concentration at the outlet. Specifically, injection should be stopped when it is confirmed that the ozone gas concentration at the outlet exceeds half the ozone gas concentration at the injection port. If ozone gas is injected further after the ozone gas concentration at the outlet exceeds half, the acid value of the treated material will increase, which may adversely affect the nickel catalyst in the subsequent hydrogenation process (2).

[0022] In this process, the acid value of the treated material treated with the resulting ozone gas is kept below 15 mg KOH / g. If the acid value exceeds 15 mg KOH / g, it may adversely affect the nickel catalyst used in the subsequent hydrogenation step (2), causing the hydrogenation reaction to slow down rapidly or preventing hydrogen absorption from occurring. The preferred upper limit for the above acid value is 10 mg KOH / g.

[0023] The injection speed of the ozone gas described above is not particularly limited, although it is also affected by the concentration of the ozone gas. It is preferable that the following conditions (A) and (B) are met: Condition (A): An injection speed that allows control of the processing temperature (40°C or lower). Condition (B): An injection speed that allows sufficient contact with the oleyl alcohol. If the injection speed of the ozone gas is too fast, the heat generated during ozone gas treatment will be excessive, resulting in an inability to control the processing temperature under condition (A), which may lead to an increase in the acid value of the treated material. Also, if the ozone gas under condition (B) and the oleyl alcohol do not come into sufficient contact, the ozone gas will be discharged from the outlet in its gaseous state, and the ozone gas concentration at the outlet may reach the above-mentioned end-of-treatment concentration without sufficient treatment of the oleyl alcohol.

[0024] By blowing ozone gas into oleyl alcohol under the conditions described above, a product treated with ozone gas having an acid value of 15 mg KOH / g or less can be efficiently prepared.

[0025] <(2) Hydrogenation Step> In the method for producing 1,9-nonanediol of the present invention, in step (2) hydrogenation, the treated product treated with ozone gas in the presence of a nickel catalyst is hydrogenated.

[0026] The nickel catalysts mentioned above are preferably Raney nickel catalysts and / or supported nickel catalysts, and materials for supporting the nickel include diatomaceous earth, silica, alumina, and activated carbon. Among supported nickel catalysts, there are also stabilized nickel catalysts that have been improved to facilitate handling. When using such stabilized nickel catalysts, it is necessary to perform an activation treatment such as hydrogenating the catalyst surface beforehand. By using the above nickel catalysts, 1,9-nonanediol can be produced with high selectivity.

[0027] Furthermore, (2) the reaction temperature for the hydrogenation step is preferably 50 to 100°C. If the reaction temperature is below 50°C, a sufficient hydrogenation reaction may not occur, and if it exceeds 100°C, the treated material treated with ozone gas may self-decompose.

[0028] The amount of catalyst is preferably 5% by mass or more relative to 100% by mass of oleyl alcohol. If it is less than 5% by mass, the hydrogenation of the treated material may be insufficient. A more preferable amount of catalyst is 10% by mass or more.

[0029] Furthermore, a solvent may be used in steps (1) and (2) above. The solvent is not particularly limited as long as it is stable with respect to hydrogen, but alcohols are preferred. Examples of alcohols include methyl alcohol, ethyl alcohol, 1-propyl alcohol, butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, hexyl alcohol, cyclohexyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, and nonyl alcohol.

[0030] In the present invention, it is preferable to carry out the hydrogenation step (2) above under hydrogen pressure conditions of 0.6 MPa or higher. If the hydrogen pressure is less than 0.6 MPa, the hydrogenation of the treated material treated with ozone gas may be insufficient, which is undesirable. A more preferable lower limit for the above hydrogen pressure is 0.9 MPa.

[0031] By performing the above-described steps of (1) blowing in ozone gas and (2) hydrogenation, a crude reaction product containing 1,9-nonanediol is produced. According to the present invention, the selectivity for 1,9-nonanediol is preferably 20% or more, and more preferably 25% or more. Here, the selectivity is calculated by the following formula: (Selectivity) = (GC% of 1,9-nonanediol) × 100 / (100% - GC% of cetyl alcohol and stearyl alcohol)

[0032] In this invention, it is preferable that the above steps (1) blowing in ozone gas and (2) hydrogenation be carried out in the same reactor, and more preferably that the steps (1) blowing in ozone gas and (2) hydrogenation be carried out continuously in the same reactor. By carrying out the steps continuously in the same reactor, 1,9-nonanediol can be efficiently produced without moving the ozone-treated material.

[0033] In the present invention, it is preferable to subject the crude reaction product containing 1,9-nonanediol obtained in step (2) hydrogenation to distillation. The distillation method is not particularly limited and conventionally known methods can be used. By performing such distillation, 1,9-nonanediol of high purity can be produced.

[0034] This specification discloses the following: Disclosure (1) is a method for producing 1,9-nonanediol, comprising the steps of (1) blowing ozone gas into oleyl alcohol, wherein the ozone gas concentration at the outlet is blown in until it exceeds 1 / 2 the ozone gas concentration at the inlet, and the acid value of the treated product treated with the ozone gas is 15 mg KOH / g or less; and (2) hydrogenating the treated product treated with the ozone gas in the presence of a nickel catalyst. Disclosure (2) is the method for producing 1,9-nonanediol according to Disclosure (1), wherein the nickel catalyst is a Raney nickel catalyst and / or a supported nickel catalyst. Disclosure (3) is the method for producing 1,9-nonanediol according to Disclosure (1) or (2), wherein the reaction temperature of the hydrogenation step in (2) is 50 to 100°C. Disclosure (4) is a method for producing 1,9-nonanediol according to any one of Disclosures (1) to (3), wherein the oleyl alcohol temperature in step (1) blowing in ozone gas is 40°C or lower. Disclosure (5) is a method for producing 1,9-nonanediol according to any one of Disclosures (1) to (4), wherein a solvent is used in step (1) blowing in ozone gas and / or step (2) hydrogenation. Disclosure (6) is a method for producing 1,9-nonanediol according to Disclosure (5), wherein the solvent is an alcohol. Disclosure (7) is a method for producing 1,9-nonanediol according to any one of Disclosures (1) to (6), wherein step (2) hydrogenation is carried out under hydrogen pressure conditions of 0.6 MPa or higher. Disclosure (8) is a method for producing 1,9-nonanediol according to any one of Disclosures (1) to (7), wherein the steps of (1) blowing in ozone gas and (2) hydrogenation are carried out in the same reactor. Disclosure (9) is a method for producing 1,9-nonanediol according to Disclosure (8), wherein the steps of (1) blowing in ozone gas and (2) hydrogenation are carried out continuously in the same reactor. Disclosure (10) is a method for producing 1,9-nonanediol according to any one of Disclosures (1) to (9), wherein the crude reaction product containing 1,9-nonanediol obtained in the step of (2) hydrogenation is subjected to distillation.Disclosure (11) is a method for producing 1,9-nonanediol according to any one of Disclosures (1) to (10), wherein the oleyl alcohol is oleyl alcohol derived from biomass.

[0035] The present invention will be further described in detail below with reference to examples, but the present invention is not limited to these examples. Compounds not specifically mentioned were commercially available or reagents.

[0036] <Acid Value> The acid value was measured in accordance with JIS K2501.

[0037] <Gas Chromatography (GC Analysis)> Instrument: Shimadzu GC-2030 Column: Agilent Technologies DB-1 30m x 0.25mm x 0.25μm Column temperature: 60-300°C (heating rate 10°C / min) Injection temperature / detector temperature: 305°C / 305°C Detector: FID Carrier gas: Helium gas Linear velocity: 27.4 cm / sec Sample: 1% by mass acetone solution Injection volume: 1 μl Here, the selectivity is calculated by the following formula: (Selectivity) = (GC% of 1,9-nonanediol) x 100 / (GC% of 100% cetyl alcohol and stearyl alcohol)

[0038] [Experimental Example 1] 300 g of oleyl alcohol (Rikakoll 90B, manufactured by Shin Nippon Rika Co., Ltd., 87 GC% purity, with 4 GC% cetyl alcohol and 2 GC% stearyl alcohol as impurities) was charged into an autoclave equipped with an ozone gas inlet and a gas outlet. After purging with nitrogen, the temperature was maintained at 10°C, and while stirring, ozone gas (concentration 45 g / m³) was introduced through the gas inlet. ３ The ozone was blown into oleyl alcohol at a rate of 4 L / min while bubbling. The ozone generator used was an SG-01A-PSA4 manufactured by Sumitomo Precision Products Co., Ltd. The ozone gas concentration of the gas coming out of the gas outlet was measured using an ozone gas concentration meter (UV OZONE MONITOR MODEL 610 manufactured by Ebara Corporation). The ozone gas concentration at the gas outlet was 23 g / m³. ３Ozone gas was blown in until [the specified condition]. The blowing time was 5.5 hours. The inside of the autoclave was replaced with nitrogen, and a small amount of the processed material treated with ozone gas was taken out as a sample, and the acid value was measured. As a result, the acid value was 6.3 mg KOH / g (see Table 1).

[0039] [Experimental Examples 2 to 4, Comparative Experimental Examples 1 to 3] It was carried out in the same manner as in Experimental Example 1 under the conditions described in Table 1. The results are shown in Table 1. Regarding Comparative Experimental Example 2, self-decomposition (abnormal heat generation) was observed during the blowing of ozone gas, and temperature control became impossible.

[0040] [Experimental Example 5] It was carried out in the same manner as in Experimental Example 1 except that half of the oleyl alcohol in Experimental Example 1 was diluted to 50% by mass with 2-propyl alcohol (IPA). The results are shown in Table 1.

[0041]

[0042] From Table 1, in Experimental Examples 1 to 5, the acid value of the processed material treated with ozone gas was 15 mg KOH / g or less, and the determination result was good. On the other hand, in Comparative Experimental Example 1, as a result of setting the temperature as high as 60°C, the acid value of the processed material treated with ozone gas increased. Furthermore, in Comparative Experimental Example 2 at a higher temperature (90°C), the processed material treated with ozone gas underwent self-decomposition (abnormal heat generation), and temperature control became impossible. In Comparative Experimental Example 3, when the blowing time of ozone gas (about 3 times) was lengthened, the acid value of the processed material treated with ozone gas increased.

[0043] [Example 1] The catalytic activity on the surface of a 40 - 50% nickel / silica gel catalyst was enhanced by reduction treatment at 150°C for 1 hour under a hydrogen pressure of 1.5 MPa atmosphere. Next, 10% by mass of the processed material treated with ozone gas obtained in Experimental Example 1 and the activated 40 - 50% nickel / silica gel catalyst were charged into an autoclave with respect to the oleyl alcohol used in Experimental Example 1, nitrogen substitution was performed, and further hydrogen substitution was performed 5 times to set the hydrogen pressure to 0.9 MPa. Then, while stirring, the temperature was raised to 60°C, and a reaction was carried out for 5 hours while maintaining a hydrogen pressure of 0.9 MPa. After the reaction, GC analysis of the reaction product was performed, and the results are shown in Table 2.

[0044] [Examples 2-9, Comparative Examples 1-6] The same procedure as in Example 1 was followed, using the conditions and catalysts described in Table 2. The results are shown in Table 2. In Example 8, half of the ozone-treated material was diluted to 50% by mass with 2-propyl alcohol (IPA).

[0045] [Example 10] 300 g of oleyl alcohol (Rikacol 90B, manufactured by Shin Nippon Rika Co., Ltd., 87 GC% purity, with 4 GC% cetyl alcohol and 2 GC% stearyl alcohol as impurities) was charged into an autoclave equipped with a gas inlet, a gas outlet, and a catalyst inlet. After purging with nitrogen, the temperature was maintained at 10°C, and while stirring, ozone gas (concentration 45 g / m³) was introduced from the gas inlet. ３ The ozone was blown into oleyl alcohol at a rate of 4 L / min while bubbling. The ozone generator used was an SG-01A-PSA4 manufactured by Sumitomo Precision Products Co., Ltd. The ozone gas concentration of the gas coming out of the gas outlet was measured using an ozone gas concentration meter (UV OZONE MONITOR MODEL 610 manufactured by Ebara Corporation). The ozone gas concentration at the gas outlet was 23 g / m³. ３ Ozone gas was blown in until the solution reached a certain level. The blowing time was 5 hours. The autoclave was then purged with nitrogen, and a small sample of the ozone-treated material was taken and its acid value was measured. The result showed an acid value of 6.3 mg KOH / g.

[0046] Next, a 40-50% nickel / diatomaceous earth catalyst, whose surface catalytic activity had been enhanced by reduction treatment at 150°C for 1 hour under a hydrogen pressure of 1.5 MPa, was charged into an autoclave at a concentration of 10% by mass relative to oleyl alcohol. Nitrogen purging and then five hydrogen purging cycles were performed to bring the hydrogen pressure to 0.9 MPa. Subsequently, the temperature was raised to 60°C while stirring, and the reaction was carried out for 5 hours while maintaining a hydrogen pressure of 0.9 MPa. After the reaction, GC analysis of the reactants was performed, and the results are shown in Table 2.

[0047]

[0048] Table 2 shows that in Examples 1 to 9, the use of a nickel catalyst resulted in a high selectivity of 25-31% for 1,9-nonanediol (theoretical selectivity of 43%), while the selectivity for 1,9-nonanediol was 0% with other hydrogenation catalysts (Comparative Examples 3 to 6).

[0049] In Comparative Examples 1 and 2, which used ozone-treated materials with high acid values ​​(Comparative Experiment Examples 1 and 3), the selectivity for 1,9-nonanediol was low, at 15% or less.

[0050] In Example 10, the steps of (1) blowing in ozone gas and (2) hydrogenation were carried out continuously in the same reactor, and the selectivity for 1,9-nonanediol was 30% (theoretical selectivity 43%), which was good.

[0051] Furthermore, cetyl alcohol is present in the starting material oleyl alcohol (Licacol 90B) and is a component that does not contribute to the hydrogenation reaction. Stearyl alcohol is also present in the starting material oleyl alcohol (Licacol 90B) and may be produced when (1) the oleyl alcohol remaining after the ozone gas blowing process is hydrogenated during the hydrogenation process.

[0052] This invention provides a novel method for producing 1,9-nonanediol efficiently with minimal environmental impact. Furthermore, it can be used in the production of biomass-derived polyesters, polyurethanes, and acrylic resins that exhibit excellent hydrolysis resistance, flexibility, pliability, and low-temperature properties.

Claims

1. A method for producing 1,9-nonanediol, comprising: (1) a step of blowing ozone gas into oleyl alcohol, wherein the ozone gas is blown in until the ozone gas concentration at the outlet exceeds 1 / 2 of the ozone gas concentration at the inlet, and the acid value of the treated product treated with the ozone gas is 15 mg KOH / g or less; and (2) a step of hydrogenating the treated product treated with the ozone gas in the presence of a nickel catalyst.

2. The method for producing 1,9-nonanediol according to claim 1, wherein the nickel catalyst is a Raney nickel catalyst and / or a supported nickel catalyst.

3. A method for producing 1,9-nonanediol according to claim 1 or 2, wherein the reaction temperature of the hydrogenation step (2) is 50 to 100°C.

4. The method for producing 1,9-nonanediol according to claim 1 or 2, wherein the temperature of the oleyl alcohol in the step of blowing in ozone gas (1) is 40°C or lower.

5. A method for producing 1,9-nonanediol according to claim 1 or 2, wherein a solvent is used in the step of (1) blowing in ozone gas and / or the step of hydrogenation.

6. The method for producing 1,9-nonanediol according to claim 5, wherein the solvent is an alcohol.

7. A method for producing 1,9-nonanediol according to claim 1 or 2, wherein the hydrogenation step (2) is carried out under a hydrogen pressure of 0.6 MPa or higher.

8. A method for producing 1,9-nonanediol according to claim 1 or 2, wherein the steps of (1) blowing in ozone gas and (2) hydrogenation are carried out in the same reactor.

9. The method for producing 1,9-nonanediol according to claim 8, wherein the steps of (1) blowing in ozone gas and (2) hydrogenation are carried out continuously in the same reactor.

10. A method for producing 1,9-nonanediol according to claim 1 or 2, wherein the crude reaction product containing 1,9-nonanediol obtained in the hydrogenation step (2) is subjected to distillation.

11. The method for producing 1,9-nonanediol according to claim 1 or 2, wherein the oleyl alcohol is biomass-derived oleyl alcohol.

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